Development of high-performance and cost-effective non-noble metal electrocatalysts is pivotal for the eco-friendly production of hydrogen through electrolysis and hydrogen energy applications. Herein, the synthesis of an unconventional nickel nitride nanostructure enriched with nitrogen vacancies (Ni3N1-x ) through plasma-enhanced nitridation of commercial Ni foam (NF) is reported. The self-supported Ni3N1-x /NF electrode can deliver a hydrogen evolution reaction (HER) activity competitive to commercial Pt/C catalyst in alkaline condition (i.e., an overpotential of 55 mV at 10 mA cm-2 and a Tafel slope of 54 mV dec-1), which is much superior to the stoichiometric Ni3N, and is the best among all nitride-based HER electrocatalysts in alkaline media reported thus far. Based on theoretical calculations, it is further verified that the presence of nitrogen vacancies effectively enhances the adsorption of water molecules and ameliorates the adsorption-desorption behavior of intermediately adsorbed hydrogen, which leads to an advanced HER activity of Ni3N1-x /NF.
Keywords: electrocatalysis; hydrogen evolution; nitrogen vacancies; plasma‐enhanced nitridation.